US3833645A - Preparation of 2-chloroethane-phosphonic acid - Google Patents
Preparation of 2-chloroethane-phosphonic acid Download PDFInfo
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- US3833645A US3833645A US00351155A US35115573A US3833645A US 3833645 A US3833645 A US 3833645A US 00351155 A US00351155 A US 00351155A US 35115573 A US35115573 A US 35115573A US 3833645 A US3833645 A US 3833645A
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- Prior art keywords
- chloroethanephosphonic
- splitting
- hydrogen chloride
- ester
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- UDPGUMQDCGORJQ-UHFFFAOYSA-N (2-chloroethyl)phosphonic acid Chemical compound OP(O)(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-N 0.000 title abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 abstract description 27
- 150000002148 esters Chemical class 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 231100000331 toxic Toxicity 0.000 description 7
- 230000002588 toxic effect Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- -1 2-chloroethyl ester Chemical class 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 239000005648 plant growth regulator Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- NLAFDAIUYHCRGU-UHFFFAOYSA-N 2-chloroethoxy(2-chloroethyl)phosphinic acid Chemical compound ClCCP(=O)(O)OCCCl NLAFDAIUYHCRGU-UHFFFAOYSA-N 0.000 description 1
- SEHJHHHUIGULEI-UHFFFAOYSA-N 2-hydroxyethylphosphonic acid Chemical compound OCCP(O)(O)=O SEHJHHHUIGULEI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/42—Halides thereof
- C07F9/425—Acid or estermonohalides thereof, e.g. RP(=X)(YR)(Hal) (X, Y = O, S; R = H, or hydrocarbon group)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
Definitions
- the present invention relates to a new process for the production of 2-chloroethanephosphonic acid by splitting the corresponding bis 2-chloroethyl ester.
- 2-haloethanephosphonic acids especially 2-chloroethanephosphonic acid
- plant growth regulators Dutch Patent Application No. 68-02633
- the prior art processes for preparing these compounds are not satisfactory because of very high operating and equipment costs and because the products obtained are not sufiiciently pure.
- those products should be used as plant growth regulators for increasing plant and fruit crops which do not contain any impurities toxic to human beings.
- a process is for instance known from German Laid- Open Applications DOS 1,768,061 and 1,768,219 which relates to the splitting of 2-chloroethanephosphonic bis-2- chloroethyl ester with anhydrous hydrogen chloride. It is however not possible to split the ester quantitatively in this manner as it has been found that the product thus obtained is considerably contaminated by the mono-2- chloroethyl ester of 2-chloroethanephosphonic acid.
- This "ice monoester derivative which is a potential source for the highly toxic 2-chloroethanol, stubbornly remains in the plant tissue for a long time and constitutes a considerable danger to the consumer because of its toxicity.
- the process according to the invention which may be carried out in a single reactor without elaborate apparatus, provides 2 chloroethanephosphonic acid in almost quantitative yield and free from toxic impurities.
- 2-chloroethanephosphonic acid is obtained in a high degree of purity and approximately quantitative yield in the stagewise splitting of 2- chloroethanephosphonic bis-Z-chloroethyl ester when splitting is carried out in a first stage with phosgene at to 220 C. and in a second stage with anhydrous hydrogen chloride at to 220 C. and the reaction product is subsequently treated with ice, water or steam at 10 to 200 C.
- the starting material is 2-chloroethanephosphonic bis- 2-chloroethyl ester which is easily obtainable by known methods from phosphorus trichloride and ethylenepxide (Houben-Weyl, Methoden der Organischen Chemie, XII/ 1, 443 (1963)).
- the ester prepared in this manner is treated in the first stage with phosgene and the reaction product is reacted without further purification direct with anhydrous hydrogen chloride and subsequently treated with water.
- This reaction sequence is illustrated for example by the following equations but it is not intended to rule out the possibility that, for instance, phosphonic anhydrides may be formed.
- This stepwise splitting of the diester of 2-chlor0ethanephosphonic acid is advantageous because it can be carried out at atmospheric pressure and without changing the re actor, i.e., with a minimum of expenditure.
- the process of the invention therefore results in a considerable simplification of the prior art method.
- Of further advantage is the short reaction period required for splitting the ester with phosgene and anhydrous hydrogen chloride.
- the process of the invention is generally carried out by preparing, by a prior art method, 2-chloroethane bis-2 chloroethyl ester and gassing it in the same reaction vessel with phosgene at 75 to 220 C., preferably 155 to 165 C., or at 175 C., for 4 to 6 hours.
- EXAMPLE 1 549.4 g. of crude 2-chloroethanephosphonic bis-2 chloroethyl ester, prepared from phosphorus trichloride and ethylene oxide, was placed in a four-necked flask equipped with stirrer, thermometer, gas supply tube and cooler and gassed at 160 C., with phosgene. The 1,2-dichloroethane which evolved was removed by distillation from the reaction vessel and collected in a flask. After 5 to 6 hours no more 1,2-dichloroethane evolved. Anhydrous hydrogen chloride was now gassed into the reaction product at 160 C. until, after 4 to 5 hours, no more 1,2- dichloroethane distilled off.
- the nuclear resonance spectrum shows no further bands in addition to the absorption bands of pure 2-chloroethanephosphonic acid.
- Example 2 The procedure of Example 1 was adopted except that phosgene was gassed in at 175 C. for 5 to 6 hours. Only 1 hour was required for the subsequent treatment with anhydrous hydrogen chloride. The yield and purity are as in Example 1.
- EXAMPLE 3 0.5 mole of 2-chloroethanephosphonic mono-Z-chloroethyl ester monochloride which is presumed to be formed 4 as an intermediate in Example 1 and is produced by the method of M. J. Kabachnik and P. A. Rossiikaya, Izvest. Akad. Nauk. S.S.S.R., 'Otdel. Khim. Nauk., 1946, 295; red C. A., 42, 7242i (1948), was treated at 160 C. with anhydrous hydrogen chloride and worked up as described in Example 1. The yield and purity are as in Example 1.
- a process for the production of 2-chloroethanephosphonic acid from 2-chloroethanephosponic bis-2-chloroethyl ester by splitting wherein splitting is carried out in a first stage with phosgene at to 220 C., and in a second stage with anhydrous hydrogen chloride at to 220 C., followed by treatment of the reaction product with ice, Water or steam at 10 to 200 C.
- stage- Wise splitting of Z-chloroethanephosphonic bis-2-chloro ethyl ester is begun with phosgene and completed by treatment with anhydrous hydrogen chloride at 155 to 165 C.
- reaction product after the splitting of the 2-chloroethanephosphonic bis-2-chloroethyl ester with phosgene and anhydrous hydrogen chloride, is hydrolyzed with Water at 60 to C. to give Z-chloroethanephosphonic acid.
- reaction product after the splitting of 2-chloroethanephosphonic mono-2-chloroethy1 ester monochloride with anhydrous hydrogen chloride, is hydrolyzed with water at 10 to 200 C., preferably 60 to 150 C., to give 2-chloroethanephosphonic acid.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
NEW PROCESS FOR THE PREPARATION OF 2-CHLOROETHANEPHOSPHONIC ACID BY SPLITTING THE CORRESPONDING BIS-2CHLOROETHYL ESTER.
Description
United States Patent O 3,833,645 PREPARATION OF Z-CHLOROETHANE- PHOSPHONIC ACID Hans Theobald, Limburgerhof, and Karl Kiehs, Lampertheim, Germany, assignors to Badische Anilin- & Soda- Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany No Drawing. Filed Apr. 16, 1973, Ser. No. 351,155 Int. Cl. C07f 9/38 U.S. Cl. 260-502.4 R 7 Claims ABSTRACT OF THE DISCLOSURE New process for the preparation of 2-chloroethanephosphonic acid by splitting the corresponding bis-2- chloroethyl ester.
The present invention relates to a new process for the production of 2-chloroethanephosphonic acid by splitting the corresponding bis 2-chloroethyl ester.
2-haloethanephosphonic acids, especially 2-chloroethanephosphonic acid, are well known as plant growth regulators (Dutch Patent Application No. 68-02633). However, the prior art processes for preparing these compounds are not satisfactory because of very high operating and equipment costs and because the products obtained are not sufiiciently pure. However, in the interests of the consumer only those products should be used as plant growth regulators for increasing plant and fruit crops which do not contain any impurities toxic to human beings.
It is known to produce 2-chloroethanephosphonic acid by hydrolysis of 2-chloroethanephosphonyl dichloride, which in turn is obtained by reacting PCl ethylene and oxygen with or without a catalyst (German Laid-Open Applications DOS 2,032,135 and 1,103,922) or by reacting POCl and ethylene (German Laid-Open Application DOS 2,032,136). However, these prior art processes involve high expenditure for equipment and only provide Z-chloroethanephosphonyl dichloride in very low yields (survey: L. Maier, Helv. Chim. Acta, 52, 1337 (1969) It is further known (German Laid-Open Application DOS 2,053,967) to prepare 2-chloroethanephosphonic acid from 2 acyloxyethanephosphonic acids or esters thereof by reaction with anhydrous hydrogen chloride. This process is however unsatisfactory because a 2-chloroethanephosphonic acid containing 15 to 25% impurities is obtained from the starting compounds which are ditiicult to isolate in the pure state.
It is furthermore known to produce 2-chloroethanephosphonic acid by splitting the corresponding diesters only the splitting of the industrially easily accessible 2- chloroethanephosphonic bis-2-chloroethyl ester being of practical value. The prior art processes have however not provided satisfactory results because it has not yet been possible to split the ester quantitatively and considerably contaminated products are obtained in spite of at times high equipment costs. These impurities are most disadvantageous because they not only have a toxic effect on plants but constitute a potential danger to the consumer of plants and fruit treated with the compounds containing them.
A process is for instance known from German Laid- Open Applications DOS 1,768,061 and 1,768,219 which relates to the splitting of 2-chloroethanephosphonic bis-2- chloroethyl ester with anhydrous hydrogen chloride. It is however not possible to split the ester quantitatively in this manner as it has been found that the product thus obtained is considerably contaminated by the mono-2- chloroethyl ester of 2-chloroethanephosphonic acid. This "ice monoester derivative, which is a potential source for the highly toxic 2-chloroethanol, stubbornly remains in the plant tissue for a long time and constitutes a considerable danger to the consumer because of its toxicity. These serious disadvantages are described in German Laid-Open Application DOS 2,050,245 are repeated in a later application, DOS 2,053,967.
According to a further process (German Laid-Open Application DOS 2,050,245) the 2 chloroethanephosphonic bis-2-chloroethyl ester is split with concentrated hydrochloric acid. However, this process is satisfactory neither from the technical and economic viewpoint nor with regard to product purity Ester splitting with concentrated hydrochloric acid not only requires extremely long reaction times, but also must be carried out under pressure necessitating the use of expensive corrosionresistant equipment. The product prepared in this manner is contaminated not only by the toxic monoester derivative but also by the toxic 2-hydroxyethanephosphonic acid which forms as a result of the long reaction times by exchange of the 2-chloro radical for a hydroxy group. These disadvantages are disclosed in German Laid- Open Application DOS 2,053,967.
In contrast to the above-mentioned processes the process according to the invention, which may be carried out in a single reactor without elaborate apparatus, provides 2 chloroethanephosphonic acid in almost quantitative yield and free from toxic impurities.
We have now found that 2-chloroethanephosphonic acid is obtained in a high degree of purity and approximately quantitative yield in the stagewise splitting of 2- chloroethanephosphonic bis-Z-chloroethyl ester when splitting is carried out in a first stage with phosgene at to 220 C. and in a second stage with anhydrous hydrogen chloride at to 220 C. and the reaction product is subsequently treated with ice, water or steam at 10 to 200 C.
The starting material is 2-chloroethanephosphonic bis- 2-chloroethyl ester which is easily obtainable by known methods from phosphorus trichloride and ethylenepxide (Houben-Weyl, Methoden der Organischen Chemie, XII/ 1, 443 (1963)). The ester prepared in this manner is treated in the first stage with phosgene and the reaction product is reacted without further purification direct with anhydrous hydrogen chloride and subsequently treated with water. This reaction sequence is illustrated for example by the following equations but it is not intended to rule out the possibility that, for instance, phosphonic anhydrides may be formed.
Cock
+ Ci-CHr-CHrCl C0;
( O OCH3-CHr-Cl (I? OH Ci-GHz-CHz-P C1-CHr-CH3-C1 HCI What is novel and extremely surprising is how easily the monochloride of 2-chloroethanephosphonic mono-2- chloroethyl ester may be split with anhydrous hydrogen chloride. After treatment with water 2-chloroethanephosphonic acid is obtained in almost quantitative yield, high purity and free from toxic impurities.
This stepwise splitting of the diester of 2-chlor0ethanephosphonic acid is advantageous because it can be carried out at atmospheric pressure and without changing the re actor, i.e., with a minimum of expenditure. The process of the invention therefore results in a considerable simplification of the prior art method. Of further advantage is the short reaction period required for splitting the ester with phosgene and anhydrous hydrogen chloride.
The process of the invention is generally carried out by preparing, by a prior art method, 2-chloroethane bis-2 chloroethyl ester and gassing it in the same reaction vessel with phosgene at 75 to 220 C., preferably 155 to 165 C., or at 175 C., for 4 to 6 hours. The crude product obtained in then treated, without further purification, at 140 to 220 C., preferably 155 to 165 C., for about 1 to hours with anhydrous hydrogen chloride. During gassing with phosgene and anhydrous hydrogen chloride the 2-chloroethanephosphonic bis-2-chloroethyl ester is split and simultaneously the alcohol component of the ester is removed by distillation from the reaction vessel as 1,2-dichloroethane, the reaction equilibrium being shifted in favor of 2-chloroethanephosphonic acid. The 1,2-dichloroethane which has been removed from the reactor is collected in a separate flask. Unreacted phosgene or hydrogen chloride is recycled to the reaction vessel and thus fully utilized. Subsequent hydrolysis of the product with ice, water or steam proceeds exothermically, temperatures of from to 200 C., preferably 60 to 150 C., being maintained.
The process of the invention is illustrated by the following examples.
EXAMPLE 1 549.4 g. of crude 2-chloroethanephosphonic bis-2 chloroethyl ester, prepared from phosphorus trichloride and ethylene oxide, was placed in a four-necked flask equipped with stirrer, thermometer, gas supply tube and cooler and gassed at 160 C., with phosgene. The 1,2-dichloroethane which evolved was removed by distillation from the reaction vessel and collected in a flask. After 5 to 6 hours no more 1,2-dichloroethane evolved. Anhydrous hydrogen chloride was now gassed into the reaction product at 160 C. until, after 4 to 5 hours, no more 1,2- dichloroethane distilled off. After cooling, about 1 liter of water was added in portions, the reaction temperature rising to about 50 C. The mixture was left for 30 minutes at 60 to 90 C.; water and hydrogen chloride were then drawn off at sub-atmospheric pressure. Z-chloroethanephosphonic acid having a melting point of 65 to 70 C. was obtained in 95% yield. Analysis of the crude product provided the following data:
Calc.: C, 16.6; H, 4.1; P, 21.5; CI, 24.6. Found: C, 16.2; H, 4.2; P, 20.8; C1, 23.3.
The nuclear resonance spectrum shows no further bands in addition to the absorption bands of pure 2-chloroethanephosphonic acid.
. EXAMPLE 2 The procedure of Example 1 was adopted except that phosgene was gassed in at 175 C. for 5 to 6 hours. Only 1 hour was required for the subsequent treatment with anhydrous hydrogen chloride. The yield and purity are as in Example 1.
EXAMPLE 3 0.5 mole of 2-chloroethanephosphonic mono-Z-chloroethyl ester monochloride which is presumed to be formed 4 as an intermediate in Example 1 and is produced by the method of M. J. Kabachnik and P. A. Rossiikaya, Izvest. Akad. Nauk. S.S.S.R., 'Otdel. Khim. Nauk., 1946, 295; red C. A., 42, 7242i (1948), was treated at 160 C. with anhydrous hydrogen chloride and worked up as described in Example 1. The yield and purity are as in Example 1.
We claim:
1. A process for the production of 2-chloroethanephosphonic acid from 2-chloroethanephosponic bis-2-chloroethyl ester by splitting wherein splitting is carried out in a first stage with phosgene at to 220 C., and in a second stage with anhydrous hydrogen chloride at to 220 C., followed by treatment of the reaction product with ice, Water or steam at 10 to 200 C.
2. A process as claimed in claim 1 wherein splitting of the 2-chloroethanephosphonic bis-2-chloroethyl ester with phosgene is carried out at 155 to 165 C.
3. A process as claimed in claim 1 wherein splitting of the 2-chloroethanephosphonic bis-2-chloroethyl ester with phosgene is carried out at 175 C.
4. A process as claimed in claim 1 wherein the stage- Wise splitting of Z-chloroethanephosphonic bis-2-chloro ethyl ester is begun with phosgene and completed by treatment with anhydrous hydrogen chloride at 155 to 165 C.
5. A process as claimed in claim 1 wherein the reaction product, after the splitting of the 2-chloroethanephosphonic bis-2-chloroethyl ester with phosgene and anhydrous hydrogen chloride, is hydrolyzed with Water at 60 to C. to give Z-chloroethanephosphonic acid.
6. A process as claimed in claim 5 wherein 2-chloroethanephosphonic mono-Z-chloroethyl ester monochloride is split with anhydrous hydrogen chloride at to C.
7. A process as claimed in claim 6 wherein the reaction product, after the splitting of 2-chloroethanephosphonic mono-2-chloroethy1 ester monochloride with anhydrous hydrogen chloride, is hydrolyzed with water at 10 to 200 C., preferably 60 to 150 C., to give 2-chloroethanephosphonic acid.
References Cited UNITED STATES PATENTS 3,167,574 1/ 1965 Brown et al. 260986 3,200,048 8/1965 Briggeman et al. 260986 3,600,345 8/1971 Randall et al. 260502.4 P 3,626,037 12/1971 Randall et al. 260-986 3,699,195 10/1972 Randall et al. 260502.4 R 3,775,410 11/1973 Vogel 260502.4 R
FOREIGN PATENTS 1,565,742 3/1969 France 260-502.4 R
OTHER REFERENCES Kabachnik et al.: Chem. Abstracts, vol. 42 (1948), col. 7242.
Vogt: Tetrahedron Letters, No. 15 (197-0), pp. 1281- 1284.
JOSEPH E. EVANS, Primary Examiner US. Cl. X.R.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,833,645
DATED September 3, 1974 INVENTOR(S) Hans Theobald et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
In the heading insert Claims priority,
application Germany, May 12, 1972, P 22 23 239.9---
Signed and Scaled this [SEAL] Attest:
thirtieth Day of December 1975
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2223239A DE2223239C3 (en) | 1972-05-12 | 1972-05-12 | Process for the production of 2-chloroethane phosphonic acid BASF AG, 6700 Ludwigshafen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3833645A true US3833645A (en) | 1974-09-03 |
Family
ID=5844755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00351155A Expired - Lifetime US3833645A (en) | 1972-05-12 | 1973-04-16 | Preparation of 2-chloroethane-phosphonic acid |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US3833645A (en) |
| JP (1) | JPS5550958B2 (en) |
| BE (1) | BE799431A (en) |
| CH (1) | CH570412A5 (en) |
| DE (1) | DE2223239C3 (en) |
| FR (1) | FR2184748B1 (en) |
| GB (1) | GB1422362A (en) |
| IL (1) | IL42055A (en) |
| NL (1) | NL180834C (en) |
| SU (1) | SU475782A3 (en) |
| ZA (1) | ZA733099B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3896163A (en) * | 1974-05-31 | 1975-07-22 | Amchem Prod | Purification of aliphatic phosphonic acids |
| US4728466A (en) * | 1985-10-18 | 1988-03-01 | Rhone-Poulenc Nederland B.V. | Process for the production of aliphatic phosphonic acids |
-
1972
- 1972-05-12 DE DE2223239A patent/DE2223239C3/en not_active Expired
-
1973
- 1973-04-16 US US00351155A patent/US3833645A/en not_active Expired - Lifetime
- 1973-04-16 JP JP4230173A patent/JPS5550958B2/ja not_active Expired
- 1973-04-18 IL IL42055A patent/IL42055A/en unknown
- 1973-05-07 CH CH645773A patent/CH570412A5/xx not_active IP Right Cessation
- 1973-05-08 ZA ZA733099A patent/ZA733099B/en unknown
- 1973-05-10 NL NLAANVRAGE7306543,A patent/NL180834C/en not_active IP Right Cessation
- 1973-05-11 BE BE131029A patent/BE799431A/en not_active IP Right Cessation
- 1973-05-11 GB GB2248973A patent/GB1422362A/en not_active Expired
- 1973-05-11 SU SU1920010A patent/SU475782A3/en active
- 1973-05-11 FR FR7317180A patent/FR2184748B1/fr not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3896163A (en) * | 1974-05-31 | 1975-07-22 | Amchem Prod | Purification of aliphatic phosphonic acids |
| US4728466A (en) * | 1985-10-18 | 1988-03-01 | Rhone-Poulenc Nederland B.V. | Process for the production of aliphatic phosphonic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| SU475782A3 (en) | 1975-06-30 |
| CH570412A5 (en) | 1975-12-15 |
| DE2223239B2 (en) | 1980-04-24 |
| FR2184748A1 (en) | 1973-12-28 |
| JPS4924920A (en) | 1974-03-05 |
| JPS5550958B2 (en) | 1980-12-20 |
| NL180834B (en) | 1986-12-01 |
| IL42055A (en) | 1975-06-25 |
| BE799431A (en) | 1973-11-12 |
| ZA733099B (en) | 1974-05-29 |
| NL7306543A (en) | 1973-11-14 |
| NL180834C (en) | 1987-05-04 |
| GB1422362A (en) | 1976-01-28 |
| IL42055A0 (en) | 1973-06-29 |
| DE2223239C3 (en) | 1981-01-15 |
| DE2223239A1 (en) | 1973-11-22 |
| FR2184748B1 (en) | 1978-04-21 |
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